Self-Assembly, Structural Transformation, and Guest-Binding Properties of Supramolecular Assemblies with Triangular Metal–Metal Bonded Units

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(5), P. 2524 - 2531

Published: Jan. 15, 2020

The properties of supramolecular structures are highly dependent on their metal-centered building blocks and organic linkers, thus the search for novel systems will lead to new functions applications these unique assemblies. Here, two discrete triangular trimetallic sandwich were developed construct assemblies through coordination-driven self-assembly with organosulfur ligands. A series tubelike (Tr2Pd3)4L6 (Tr = cycloheptatrienyl ring) obtained from a tripalladium complex bifunctional By replacing metal centers platinum analogue, process resulted in clean formation (Tr2Pt3)2L3 triple helicates instead species. also shown form face-capped (Tr2M3)4L4 (M Pd or Pt) tetrahedral cages when trifunctional ligands used. comprehensively analyzed by X-ray crystallography. metal-cluster-induced structural transformation between (Tr2Pd3)4L4 tubes was observed. Furthermore, cage possesses cavity allowing encapsulation guests.

Language: Английский

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Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium(III) reagents

Tetrahedron Letters, Journal Year: 2019, Volume and Issue: 60(18), P. 1281 - 1286

Published: April 4, 2019

Language: Английский

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Capture and Release of Singlet Oxygen in Coordination-Driven Self-Assembled Organoplatinum(II) Metallacycles

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(5), P. 2601 - 2608

Published: Jan. 15, 2020

Singlet oxygen (1O2), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry, and materials science. Organic conjugated aromatics serving hosts to capture release singlet have been systematically investigated over the last decades. Herein, we present a [6 + 6] organoplatinum(II) metallacycle by using ∼180° dipyridylanthracene donor ∼120° Pt(II) acceptor building blocks, which enables of with relatively high photooxygenation thermolysis rate constants. The corresponding endoperoxide was performed sensitized irradiation, resulting is stable at room temperature can be stored under ambient condition months. Upon simple heating neat inert atmosphere 120 °C for 4 h, reconverted parent form oxygen. products were characterized NMR spectroscopy electrospray ionization time-of-flight mass spectrometric analysis. Density functional theory calculations conducted order reveal frontier molecular orbital interactions reactivity. This work provides new material platform related promising applications.

Language: Английский

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Homo‐ and Heteroligand Poly‐NHC Metal Assemblies: Synthesis by Narcissistic and Social Self‐Sorting

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(48), P. 15767 - 15771

Published: Oct. 11, 2018

Abstract Homoleptic and heteroleptic cylinder‐shaped poly‐NHC metallosupramolecular assemblies [Ag 3 ( L ) 2 ](BF 4 have been prepared by control of the shape, size, electronic properties disk‐shaped trisimidazolium salts type H ‐ (BF . Both imidazolium with an electron‐deficient triazine backbone A or electron‐rich benzene D employed. Reaction Ag O yield trinuclear homoligand complexes (L= , ). However, equimolar mixtures react under social self‐sorting to give heteroligand assembly )( )](BF The same was obtained transmetallation from [Au is also demonstrated. study expands concepts narcissistic classical Werner‐type ligands organometallic NHC chemistry thereby opening new routes for construction metal increasing complexity.

Language: Английский

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A Size‐Flexible Organometallic Box for the Encapsulation of Fullerenes

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(17), P. 5682 - 5686

Published: Feb. 26, 2019

A palladium-cornered molecular square with four pyrene-bis(imidazolylidene) bridging ligands is reported. This metallo-polygon can encapsulate C60 and C70 . The X-ray diffraction structures of the empty cage as well cages complexed both fullerenes are described. fullerene encapsulation produces perturbations in structural parameters metallo-square, showing that it adjust shape its cavity to size each fullerene.

Language: Английский

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N-Heterocyclic carbenes and their precursors in functionalised porous materials

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(24), P. 13559 - 13586

Published: Jan. 1, 2021

Though N-heterocyclic carbenes (NHCs) have emerged as diverse and powerful discrete functional molecules in pharmaceutics, nanotechnology, catalysis over decades, the heterogenization of NHCs their precursors for broader applications porous materials, like metal-organic frameworks (MOFs), coordination polymers (PCPs), covalent-organic (COFs), organic (POPs), organometallic cages (POMCs) was not extensively studied until last ten years. By de novo or post-synthetic modification (PSM) methods, myriads containing building blocks were designed integrated into MOFs, PCPs, COFs, POPs POMCs to form various structures porosities. Functionalisation with significantly expands scope potential materials by tuning pore surface chemical/physical properties, providing active sites binding guest substrates realizing recyclability. In this review, we summarise discuss recent progress on synthetic structural features, promising functionalised materials. At end, a brief perspective encouraging future prospects challenges contemporary field is presented. This review will serve guide researchers design synthesize more novel precursors.

Language: Английский

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A Redox-Active Supramolecular Fe₄L₆ Cage Based on Organic Vertices with Acid–Base-Dependent Charge Tunability for Dehydrogenation Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8778 - 8788

Published: May 4, 2022

Supramolecular cage chemistry is of lasting interest because, as artificial blueprints natural enzymes, the self-assembled structures not only provide substrate-hosting biomimetic environments but also can integrate active sites in confined nanospaces for function synergism. Herein, we demonstrate a vertex-directed organic-clip chelation assembly strategy to construct metal–organic Fe4L68+ (MOC-63) incorporating 12 imidazole proton donor–acceptor motifs and four redox-active Fe centers an octahedral coordination nanospace. Different from regular supramolecular cages assembled with metal vertices, MOC-63 comprises six ditopic ligands vertices tris-chelating Fe(N∩N)3 moieties faces, thus improving its acid, base, redox robustness by virtue cage-stabilized dynamics solution. Improved dehydrogenation catalysis 1,2,3,4-tetrahydroquinoline derivatives accomplished owing effect that synergizes multiple radical species expedite intermediate conversion multistep reactions cage-confined The acid–base buffering play vital role modulating total charge state resist pH variation tune solubility among varied solvents, thereby enhancing reaction acceleration acidic conditions rendering facile recycling catalytic process.

Language: Английский

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Controllable multiple-step configuration transformations in a thermal/photoinduced reaction

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 23, 2022

Solid-state photochemical reactions of olefinic compounds have been demonstrated to represent powerful access organic cyclic molecules with specific configurations. However, the precise control stereochemistry in these remains challenging owing complex and fleeting configuration transformations. Herein, we report a unique approach regiospecific configurations C = groups intermediates by varying temperatures multiple-step thermal/photoinduced reactions, thus successfully realizing reversible ring closing/opening changes using single-crystal coordination polymer platform. All stereochemical transitions are observed situ X-ray diffraction, powder diffraction infrared spectroscopy. Density functional theory calculations allow us rationalize mechanism synergistic This can be generalized analysis possible transformations unravel detailed for any inorganic, macromolecular susceptible incorporation into platforms.

Language: Английский

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Light‐Responsive Supramolecular Liquid‐Crystalline Metallacycle for Orthogonal Multimode Photopatterning

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Nov. 15, 2023

Abstract The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in chemistry and materials science, because SCCs can serve as promising platforms for the incorporation multiple functional building blocks. Herein, we report a light‐responsive liquid‐crystalline metallacycle that constructed by coordination‐driven self‐assembly. By exploiting its fascinating liquid crystal features, bright emission properties, facile photocyclization capability, unique system with spatially‐controlled fluorescence‐resonance energy transfer (FRET) built through introduction photochromic spiropyran derivative, which led to realization first example orthogonal three‐modes, namely holography, fluorescence, photochromism.

Language: Английский

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Metallacages and Covalent Cages for Biological Imaging and Therapeutics

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(4), P. 1061 - 1082

Published: March 8, 2023

Due to their precise three-dimensional structures and tunable cavities, metallacages covalent cages have been widely used in various fields, such as catalysis, separation, sensing, biomedicine. As a result of the unique pattern directed synthesis modular assembly, can be modified many different ways construct stimuli-responsive for marker detection imaging biological applications. Additionally, agents drugs loaded into cavity achieve disease diagnosis treatment. This Review summarizes recent advances applications presents representative examples therapeutics. The problems future development directions are emphasized, which may provide clear guidance design application controllable diagnostic reagents.

Language: Английский

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